CN118005391A - Low-resistivity electro-fused chrome corundum and preparation method thereof, refractory lining and high-temperature furnace - Google Patents
Low-resistivity electro-fused chrome corundum and preparation method thereof, refractory lining and high-temperature furnace Download PDFInfo
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- CN118005391A CN118005391A CN202410425254.1A CN202410425254A CN118005391A CN 118005391 A CN118005391 A CN 118005391A CN 202410425254 A CN202410425254 A CN 202410425254A CN 118005391 A CN118005391 A CN 118005391A
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- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 title claims abstract description 126
- 229910052593 corundum Inorganic materials 0.000 title claims abstract description 88
- 239000010431 corundum Substances 0.000 title claims abstract description 80
- 238000002360 preparation method Methods 0.000 title abstract description 16
- 239000011651 chromium Substances 0.000 claims abstract description 73
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 64
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims abstract description 45
- 239000011029 spinel Substances 0.000 claims abstract description 37
- 229910052596 spinel Inorganic materials 0.000 claims abstract description 37
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 34
- 239000004576 sand Substances 0.000 claims abstract description 34
- 229910052845 zircon Inorganic materials 0.000 claims abstract description 29
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 claims abstract description 29
- 239000000843 powder Substances 0.000 claims abstract description 26
- 229910000029 sodium carbonate Inorganic materials 0.000 claims abstract description 22
- 229910001845 yogo sapphire Inorganic materials 0.000 claims abstract description 8
- 238000002844 melting Methods 0.000 claims description 57
- 230000008018 melting Effects 0.000 claims description 56
- 238000005266 casting Methods 0.000 claims description 48
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 47
- 239000011230 binding agent Substances 0.000 claims description 22
- 238000000137 annealing Methods 0.000 claims description 20
- 239000006104 solid solution Substances 0.000 claims description 20
- 239000000919 ceramic Substances 0.000 claims description 12
- 239000000243 solution Substances 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 11
- 239000013078 crystal Substances 0.000 claims description 10
- -1 zrO 2≥65% Chemical compound 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 8
- 229910052681 coesite Inorganic materials 0.000 claims description 7
- 229910052906 cristobalite Inorganic materials 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- 230000002093 peripheral effect Effects 0.000 claims description 7
- 239000000377 silicon dioxide Substances 0.000 claims description 7
- 229910052682 stishovite Inorganic materials 0.000 claims description 7
- 229910052905 tridymite Inorganic materials 0.000 claims description 7
- 238000012545 processing Methods 0.000 claims description 6
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 4
- 229910019142 PO4 Inorganic materials 0.000 claims description 4
- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical compound O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 4
- 239000010452 phosphate Substances 0.000 claims description 4
- 238000000748 compression moulding Methods 0.000 claims description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims 1
- 229910052782 aluminium Inorganic materials 0.000 claims 1
- 239000011819 refractory material Substances 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 description 22
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 21
- 229910052760 oxygen Inorganic materials 0.000 description 21
- 239000001301 oxygen Substances 0.000 description 21
- QQHSIRTYSFLSRM-UHFFFAOYSA-N alumanylidynechromium Chemical compound [Al].[Cr] QQHSIRTYSFLSRM-UHFFFAOYSA-N 0.000 description 18
- 235000017550 sodium carbonate Nutrition 0.000 description 18
- 238000007664 blowing Methods 0.000 description 16
- 239000007788 liquid Substances 0.000 description 16
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 13
- 239000012535 impurity Substances 0.000 description 12
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 12
- 239000000463 material Substances 0.000 description 12
- 239000011521 glass Substances 0.000 description 11
- 238000009825 accumulation Methods 0.000 description 8
- 238000010309 melting process Methods 0.000 description 8
- 238000004321 preservation Methods 0.000 description 8
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 7
- 229910000423 chromium oxide Inorganic materials 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 239000000395 magnesium oxide Substances 0.000 description 7
- 239000007864 aqueous solution Substances 0.000 description 6
- 230000009286 beneficial effect Effects 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 238000007670 refining Methods 0.000 description 5
- 239000011449 brick Substances 0.000 description 4
- 238000011161 development Methods 0.000 description 4
- 230000004927 fusion Effects 0.000 description 4
- 238000001556 precipitation Methods 0.000 description 4
- 238000003825 pressing Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 239000000155 melt Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 239000006060 molten glass Substances 0.000 description 3
- 230000009257 reactivity Effects 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000004115 Sodium Silicate Substances 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 description 2
- RGPUVZXXZFNFBF-UHFFFAOYSA-K diphosphonooxyalumanyl dihydrogen phosphate Chemical compound [Al+3].OP(O)([O-])=O.OP(O)([O-])=O.OP(O)([O-])=O RGPUVZXXZFNFBF-UHFFFAOYSA-K 0.000 description 2
- 230000003628 erosive effect Effects 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 238000012423 maintenance Methods 0.000 description 2
- 229910052863 mullite Inorganic materials 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 239000010970 precious metal Substances 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical group [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 2
- 229910052911 sodium silicate Inorganic materials 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 239000007767 bonding agent Substances 0.000 description 1
- 230000003139 buffering effect Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010891 electric arc Methods 0.000 description 1
- 230000006355 external stress Effects 0.000 description 1
- 239000000156 glass melt Substances 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000002285 radioactive effect Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 230000035882 stress Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000008646 thermal stress Effects 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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Abstract
The invention relates to the technical field of refractory materials, in particular to low-resistivity electro-fused chrome corundum, a preparation method thereof, a refractory lining and a high-temperature furnace. The low-resistivity electro-fused chrome corundum is mainly prepared from the following components in percentage by mass: 39% -45% of zircon sand, 20% -24% of industrial alumina powder, 3% -6% of rho-Al 2O3, 24% -27% of chromium source, 3% -6% of spinel and 2% -2.5% of sodium carbonate; the chromium source comprises electrofused chromium and/or chromium green; in the spinel, mgO is more than or equal to 12 percent and Fe 2O3≥40%,Al2O3 is more than or equal to 30 percent according to mass percent. The low-resistivity electro-fused chrome corundum provided by the invention has low resistivity.
Description
Technical Field
The invention relates to the technical field of refractory materials, in particular to low-resistivity electro-fused chrome corundum, a preparation method thereof, a refractory lining and a high-temperature furnace.
Background
The refractory lining resistivity of the bottom feed opening of the ceramic electric melting furnace is too high, so that glass liquid is easily accumulated in the feed opening, the normal and efficient operation of a glass solidification process is affected, and the feed opening is usually required to be dredged every a period of time. However, ceramic electric melting furnaces process highly radioactive nuclear waste solutions, which have strong radioactivity, and are not accessible to humans. Therefore, mechanical control is required to be performed remotely to perform accumulation and dredging of the glass feed liquid at the feed opening, and the operation is complicated and additional research and development and cost investment are required.
Therefore, the electro-fused chrome corundum material with smaller resistivity is used for refractory bricks of the feed opening at the bottom of the ceramic electric melting furnace, so that the accumulation of noble metal and feed liquid is reduced, the dredging operation of the feed opening and the development cost of dredging equipment are reduced, and the electro-fused chrome corundum material has important significance.
In view of this, the present invention has been made.
Disclosure of Invention
The first object of the invention is to provide low-resistivity electro-fused chrome corundum, which has smaller resistivity, is used for refractory bricks at a feed opening at the bottom of a ceramic electro-melting furnace, can effectively reduce precious metal and feed liquid accumulation, and can reduce the operation of dredging the feed opening and the development cost of dredging equipment.
The second aim of the invention is to provide a preparation method of low-resistivity electro-fused chrome corundum, which has the advantages of simplicity, easiness, suitability for mass production and the like.
The third object of the present invention is to provide a refractory lining which has a low resistivity and can be used for a bottom feed opening of a ceramic electric melting furnace, and to solve the problem of accumulation of molten glass in the feed opening due to an excessively high resistivity of the refractory lining in the prior art.
A fourth object of the present invention is to provide a high temperature furnace which has high working efficiency and low maintenance cost.
In order to achieve the above object of the present invention, the following technical solutions are specifically adopted:
The invention firstly provides low-resistivity electro-fused chrome corundum, which is mainly prepared from the following components in percentage by mass: 39% -45% of zircon sand, 20% -24% of industrial alumina powder, 3% -6% of rho-Al 2O3, 24% -27% of chromium source, 3% -6% of spinel and 2% -2.5% of sodium carbonate;
Wherein the chromium source comprises electrofused chromium and/or chromium green;
In the spinel, mgO is more than or equal to 12% and Fe 2O3≥40%,Al2O3 is more than or equal to 30% in percentage by mass.
Preferably, in the zircon sand, zrO 2≥65%,SiO2 is more than or equal to 32% by mass percent.
Preferably, in the electrofused chromium, cr 2O3 is more than or equal to 99 percent by mass percent.
Preferably, in the chromium green, cr 2O3 is more than or equal to 99.5 percent by mass percent.
Preferably, the size of part of crystal grains of the aluminum-chromium solid solution in the low-resistivity electro-fused chrome corundum is 250-350 mu m.
Preferably, the low-resistivity electro-fused chrome corundum has the resistivity of less than or equal to 120 Ω & lt, cm at 1100 ℃, the resistivity of less than or equal to 140 Ω & lt, cm at 1000 ℃, the resistivity of less than or equal to 200 Ω & lt, cm at 900 ℃, the resistivity of less than or equal to 250 Ω & lt, cm at 800 ℃ and the resistivity of less than or equal to 480 Ω & lt, cm at 700 ℃.
The invention further provides a preparation method of the low-resistivity electro-fused chrome corundum, which comprises the following steps:
Uniformly mixing zircon sand, industrial alumina powder, rho-Al 2O3, a chromium source, spinel, sodium carbonate and a binding agent, and then performing compression molding and drying to obtain a rough blank; and (3) melting the rough blank, and then casting, insulating and annealing to obtain the low-resistivity electro-fused chromium corundum.
Preferably, the binding agent comprises at least one of an aqueous silicate solution and an aqueous phosphate solution.
Preferably, the mass of the binding agent is 8% -10% of the sum of the mass of the zircon sand, the industrial alumina powder, the rho-Al 2O3, the chromium source, the spinel and the sodium carbonate.
Preferably, the method further comprises the step of processing after the thermal annealing, wherein the processing comprises: and removing the peripheral part of the heat-insulating annealed casting body from the surface to the inside by 50-100 mm, and reserving the middle part of the casting body.
The invention also provides a refractory lining comprising the low-resistivity electro-fused chrome corundum.
The invention also provides a high-temperature furnace, which comprises the refractory lining;
the high temperature furnace comprises a ceramic electric melting furnace.
Compared with the prior art, the invention has the beneficial effects that:
the low-resistivity electro-fused chrome corundum provided by the invention has low resistivity, is used for refractory bricks of a feed opening at the bottom of a ceramic electric melting furnace, can effectively reduce precious metal and feed liquid accumulation, and can reduce the dredging operation of the feed opening and the development cost of dredging equipment.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are needed in the description of the embodiments or the prior art will be briefly described, and it is obvious that the drawings in the description below are some embodiments of the present invention, and other drawings can be obtained according to the drawings without inventive effort for a person skilled in the art.
FIG. 1 is an SEM image of low resistivity electro-fused chrome corundum made in example 1 provided by the present invention;
FIG. 2 is an SEM image of low resistivity electro-fused chrome corundum made in example 2 provided by the present invention.
Detailed Description
The technical solution of the present invention will be clearly and completely described below with reference to the accompanying drawings and detailed description, but it will be understood by those skilled in the art that the examples described below are some, but not all, examples of the present invention, and are intended to be illustrative of the present invention only and should not be construed as limiting the scope of the present invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
In the present invention, unless specifically stated otherwise, the terms "first", "second", "third", "fourth", etc. are used for descriptive purposes only and are not to be construed as indicating or implying a relative importance or quantity or as implicitly indicating the importance or quantity of the indicated technical feature. Moreover, the terms "first," "second," "third," "fourth," and the like are used for non-exhaustive list description purposes only, and are not to be construed as limiting the number of closed forms.
The terms "comprising" and "including" as used herein mean open ended or closed ended, unless otherwise noted. For example, the terms "comprising" and "comprises" may mean that other components not listed may be included or included, or that only listed components may be included or included.
In the present invention, "one or more" or "at least one" means any one, any two or more of the listed items unless specifically stated otherwise. Wherein "several" means any two or more.
In a first aspect, the invention provides low-resistivity electro-fused chrome corundum, which is mainly prepared from the following components in percentage by mass: 39% -45% of zircon sand, 20% -24% of industrial alumina powder, 3% -6% of rho-Al 2O3, 24% -27% of chromium source, 3% -6% of spinel and 2% -2.5% of sodium carbonate;
Wherein the zircon sand comprises, but is not limited to, any one of 39%, 40%, 41%, 42%, 43%, 44%, 45% or any range between the two by mass percent. The industrial alumina powder includes, but is not limited to, any one of a point value or a range value between any two of 20%, 21%, 22%, 23%, 24% by mass. ρ -Al 2O3 includes, but is not limited to, any one of 3%, 4%, 5%, 6% by mass of point values or range values between any two. The chromium source includes, but is not limited to, any one of 24%, 25%, 26%, 27% spot value or any range value therebetween in mass percent. Spinel includes, but is not limited to, any one of 3%, 4%, 5%, 6% point values or any range between the two values by mass percent. The sodium carbonate comprises any one point value or range value between any two points of 2%, 2.1%, 2.2%, 2.3%, 2.4% and 2.5% by mass percent.
Wherein the chromium source comprises electrofused chromium (i.e., electrofused chromium oxide) and/or chromium green (also known as chromium oxide green).
When the chromium source includes both electrofused chromium and chromium green, any mass ratio of the two may be used.
Preferably, the chromium source comprises 5-10% of chromium green (namely, the addition amount of the chromium green in the preparation raw material of the low-resistivity electro-fused chromium corundum is 5-10% by mass percent) in percentage by mass, and the reactivity of the chromium green is higher than that of the electro-fused chromium, so that the generation activity of an aluminum-chromium solid solution in the process of the melting annealing reaction can be ensured.
In the spinel, mgO is more than or equal to 12 percent, fe 2O3≥40%,Al2O3 is more than or equal to 30 percent, and the balance is impurities according to mass percent.
The low-resistivity electro-fused chrome corundum has small resistivity, can be used for refractory bricks of a feed opening at the bottom of a ceramic electric melting furnace, can effectively reduce the accumulation of noble metal and feed liquid, and can reduce the dredging operation of the feed opening and the development cost of dredging equipment. Solves the problem of accumulation of molten glass at a feed opening caused by overhigh resistivity of a refractory lining in the prior art.
Specifically, by adding rho-Al 2O3, the reactivity of the alumina with the chromium oxide in the annealing process can be improved, so that the precipitation of the aluminum-chromium solid solution is more complete, the precipitation activity is increased, and the aluminum-chromium solid solution monocrystal is taken as a crystal nucleus, so that the fusion growth between adjacent solid solutions can be promoted to become a larger aluminum-chromium solid solution, the crystal boundary is reduced, and the resistivity of the fused chromium corundum is further reduced.
By introducing spinel into the raw materials, the use of pre-synthesized spinel changes the condition that chemical components in the low-resistivity electro-fused chrome corundum are singly introduced, the molten liquid level of the added spinel is more stable in the melting process, the control of the melting current is more stable, and the uniformity of the molten liquid is obviously improved. Meanwhile, magnesium oxide and ferric oxide are introduced in a spinel form, so that the crystallization phase precipitation temperature of an aluminum-chromium solid solution in a melt is reduced, the reactivity of the aluminum-chromium solid solution is improved, the grain size of the aluminum-chromium solid solution is increased, the secondary grain growth phenomenon is more obvious, and the grain boundary is reduced, so that the resistivity of the material is reduced; and the composite introduction of spinel reduces the amount of Fe 2O3 reduced into iron, so that the phase composition of the electro-fused chrome corundum is more favorable for resisting glass melt erosion.
Wherein, zircon sand provides ZrO 2 and SiO 2 required by electro-fused chrome corundum; the addition of sodium carbonate provides Na 2 O required by electro-fused chrome corundum, reduces the melting temperature, is beneficial to reducing the difference between internal stress and external stress in the annealing process of the material, and Na 2 O can promote the generation of a glass phase and inhibit the generation of a mullite phase, so that the effects of buffering and absorbing thermal stress and reducing the generation of cracks are achieved; the generation of the glass phase and the inhibition of the generation of the mullite phase are both beneficial to improving the conductivity of the fused chrome corundum at a high temperature state and reducing the high-temperature resistivity of the fused chrome corundum, so that the addition amount of sodium carbonate can be improved on the basis of not affecting the use performance of other high temperatures at the temperature of 1100-1200 ℃, namely the Na 2 O content in the fused chrome corundum is improved.
In some specific embodiments, zrO 2≥65%,SiO2 is more than or equal to 32% by mass and the balance is impurities in the zircon sand.
In some specific embodiments, cr 2O3 is more than or equal to 99% by mass in the electrofused chromium.
In some specific embodiments, cr 2O3 is greater than or equal to 99.5% by mass in the chromium green.
The raw materials with the chemical composition can further reduce the resistivity of the electro-fused chrome corundum.
In some specific embodiments, the size of the partial grains (larger grains) of the aluminum-chromium solid solution in the low-resistivity electro-fused chromia-corundum is 250-350 μm, including but not limited to a point value of any one of 250 μm, 260 μm, 280 μm, 300 μm, 320 μm, 330 μm, 350 μm or a range value between any two, wherein the larger grains with the above sizes are formed by secondary long large fusion of a plurality of (e.g. 3-4) aluminum-chromium solid solution primary crystals. The larger aluminum-chromium solid solution crystal grains are beneficial to reducing the resistivity of the electro-fused chrome corundum.
In some embodiments, the low resistivity fused chrome corundum has a resistivity of 120 Ω cm or less at 1100 ℃, including, but not limited to, a point value of any one or a range between any two of 110 Ω cm, 105 Ω cm, 100 Ω cm, 95 Ω cm, 94 Ω cm, 91 Ω cm, 90 Ω cm; the low-resistivity electro-fused chrome corundum has the resistivity less than or equal to 140 Ω & cm at 1000 ℃ and comprises any point value or range value between any two of 138 Ω & cm, 130 Ω & cm, 120 Ω & cm, 110 Ω & cm, 108 Ω & cm, 104 Ω & cm and 100 Ω & cm; the resistivity of the low-resistivity electro-fused chrome corundum is less than or equal to 200 Ω & cm at 900 ℃, including but not limited to any one point value or range value between any two of 180 Ω & cm, 160 Ω & cm, 150 Ω & cm, 146 Ω & cm and 140 Ω & cm; the low-resistivity electro-fused chrome corundum has the resistivity less than or equal to 250 Ω & cm at 800 ℃ and comprises any point value or range value between any two of 242 Ω & cm, 238 Ω & cm, 231 Ω & cm, 230 Ω & cm, 228 Ω & cm, 226 Ω & cm and 220 Ω & cm; the low resistivity fused chrome corundum has a resistivity of less than or equal to 480 Ω.cm at 700 ℃, including but not limited to any one of 476 Ω.cm, 450 Ω.cm, 430 Ω.cm, 421 Ω.cm, 410 Ω.cm, 400 Ω.cm, 399 Ω.cm, 398 Ω.cm, or a range of values therebetween.
The low-resistivity electro-fused chrome corundum provided by the invention has low resistivity, and can be used for a refractory lining of a furnace bottom feed opening of a ceramic electric melting furnace to solve the problems of low working efficiency, complex operation and high cost caused by accumulation of glass liquid in the feed opening.
In a second aspect, the invention provides a preparation method of the low-resistivity electro-fused chrome corundum, which comprises the following steps:
Uniformly mixing zircon sand, industrial alumina powder, rho-Al 2O3, a chromium source, spinel, sodium carbonate and a binding agent, and then performing compression molding and drying to obtain a rough blank; and (3) melting the rough blank, and then casting, insulating and annealing to obtain the low-resistivity electro-fused chromium corundum.
According to the method, the rho-Al 2O3, spinel and other high-activity raw materials are added, the melting current can be increased to 7000-8000A on the premise of reducing the voltage, the melting temperature and the casting temperature are increased, growth of an aluminum-chromium solid solution monocrystal and further fusion growth of secondary crystals are facilitated, the crystal boundary is reduced, defects such as material pores are reduced, and the resistivity of fused chromium corundum is further reduced.
Meanwhile, mgO and Fe 2O3 are introduced into the spinel, so that the precipitation activities of phases such as aluminum chromium solid solution, monoclinic zirconia and spinel are increased in thermodynamic angle, mgO and Fe 2O3 exist in a glass phase, the composition of the glass phase is improved, the content of the glass phase is increased, and the conductivity is improved, so that the resistivity of fused chrome corundum is reduced.
But the high-temperature resistivity of the electric melting chrome corundum is not lower and better, the electric melting chrome corundum should be in line with the fact that the resistivity of a furnace lining material of an electric melting furnace is far greater than that of an electrode and molten glass to be melted, so that the electric melting furnace current is prevented from flowing to the furnace lining, heat power loss is avoided, and normal melting of glass and normal service life of the furnace lining material are affected.
In some embodiments, the binding agent is an inorganic salt that does not introduce additional impurities.
Preferably, the binder comprises at least one of an aqueous silicate solution and an aqueous phosphate solution, with which impurities of other chemical components may not be additionally introduced.
Wherein, the function of the bonding agent is: the initial strength is provided for the rough blank, the crushed materials are not all powder or lump materials, and the unstable current caused by the scattering of components due to excessive powder of the materials or excessive lump materials during melting and feeding is avoided.
In some specific embodiments, the mass of the binding agent is 8% -10% of the sum of the mass of the zircon sand, the industrial alumina powder, the ρ -Al 2O3, the chromium source, the spinel, and the soda ash, including, but not limited to, any one of the point values of 8%, 9%, 10%, or a range of values between any two.
In some embodiments, the silicate aqueous solution or the phosphate aqueous solution has a mass fraction of 30% -50%, including but not limited to any one of 30%, 35%, 40%, 45%, 50% or a range between any two.
In some embodiments, the drying is to a moisture content of the green body of less than or equal to 1.5% (mass fraction).
In some specific embodiments, the rough blank is crushed before the melting, which is favorable for stably controlling the melting current and uniformly melting the melt.
In some specific embodiments, the melting temperature is 2200-2400 ℃, including but not limited to a point value or a range value between any two of 2200 ℃, 2250 ℃, 2300 ℃, 2350 ℃, 2400 ℃; the melting time is 150-180 min, including but not limited to any one of point values or range values between any two of 150min, 160min, 170min and 180 min; the feeding time during melting is 8-10 min.
In some embodiments, the power regime control during the melting process: starting an arc with a high voltage of 340-360V, controlling the current to 3000-4000A, melting for 20-30 min, gradually reducing the voltage to 180-240V, and controlling the current to 5000-8000A; oxygen is blown for 2-3 times in the melting process, the first oxygen blowing is performed after 110-150 min of melting, each time oxygen blowing is performed for 3min, the oxygen blowing pressure is 0.4-0.6 MPa, and refining is continued for 8-15 min after each time oxygen blowing.
The sectional control of voltage and current is based on the characteristics of the raw materials of the fused chrome corundum, the initial stage has no molten liquid, the conductivity is poor, the current can be obtained only by high voltage, the raw materials are fused, and after the material feeding is finished or the molten liquid in an electric arc furnace is more, the voltage is reduced so as to control the current and the fusion temperature to be in a controllable range. If the current is too high, the melting process is not easy to control, and the excessive temperature of the melt is easy to cause excessive burning or excessive casting temperature to cause sand erosion, and the problem of high porosity of the casting mould is solved.
In some embodiments, the casting temperature is 1950-2150 ℃, including but not limited to any one of 1950 ℃, 2000 ℃, 2050 ℃, 2100 ℃ or a range between any two; the casting flow rate is 7-20 kg/s, including but not limited to a point value of any one of 7kg/s, 9kg/s, 10kg/s, 12kg/s, 15kg/s, 17kg/s, 20kg/s or a range value between any two.
In some specific embodiments, the period of the soak annealing is 18-25 days, including but not limited to any one of 18 days, 20 days, 23 days, 25 days, or a range between any two. It will be appreciated that during the soak anneal, the temperature of the cast product drops at a rate.
In some embodiments, the soak anneal is followed by a processing step. The processing specifically comprises the following steps: and removing the peripheral part of the annealed casting body from the surface to the inside by 50-100 mm, and reserving the middle part of the casting body to obtain the low-resistivity electro-fused chromium corundum with small porosity, compact structure and meeting the requirements of the aluminum-chromium solid solution crystal grain size and the resistivity.
In a third aspect, the invention provides a refractory lining comprising the low resistivity electro-fused chromite corundum.
The refractory lining has low resistivity, can be used for a furnace bottom feed opening of a ceramic electric melting furnace, and solves the problem that glass liquid is accumulated at the feed opening due to the fact that the resistivity of the refractory lining is too high in the prior art.
In a fourth aspect, the invention provides a high temperature furnace comprising the refractory lining.
In some embodiments, the high temperature furnace includes, but is not limited to, a ceramic electric furnace.
The high-temperature furnace has high working efficiency and low maintenance cost.
Embodiments of the present invention will be described in detail below with reference to examples, but it will be understood by those skilled in the art that the following examples are only for illustrating the present invention and should not be construed as limiting the scope of the present invention. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
The industrial alumina powder used in the embodiments of the invention is calcined alpha alumina with alpha-Al 2O3 as the main crystal phase, and YS/89-2011 standard is implemented.
Example 1
The preparation method of the low-resistivity electro-fused chrome corundum provided by the embodiment comprises the following steps:
(1) Weighing 42% of zircon sand, 22% of industrial alumina powder, 3% of rho-Al 2O3, 11% of electrofused chromium, 14% of chromium oxide green, 6% of spinel and 2% of sodium carbonate according to mass percentage to obtain a mixed raw material. Wherein, the spinel consists of the following components in percentage by mass: 12.97% of MgO, 2O345.23%,Al2O3 37.26% of Fe and the balance of impurities. The zircon sand consists of the following components in percentage by mass: zrO 265.49%,SiO2 32.58.58%, the balance being impurities. The mass percentage of Cr 2O3 in the electrofused chromium is 99.10 percent. The mass percentage of Cr 2O3 in the chromium green is 99.57 percent. The binding agent is sodium silicate aqueous solution with the mass fraction of 35%, and the mass of the binding agent is 9% of the sum of the mass of zircon sand, industrial alumina powder, rho-Al 2O3, chromium source, spinel and sodium carbonate.
And uniformly mixing the mixed raw materials with a binding agent, pressing for forming, drying to obtain a green body with the water content of 1.5wt.%, and crushing the green body until the granularity is less than 40mm.
(2) Melting the crushed rough blank obtained in the step (1), and controlling a melting power system: starting an arc at a high voltage of 360V, controlling the current to be 3000-3500A (the current fluctuation does not exceed the range), after melting for 20min, gradually reducing the voltage to 220V, and controlling the current to be 6000-6500A (the current fluctuation does not exceed the range); oxygen is blown for 2 times in the melting process, the first oxygen blowing is performed after melting for 120min, the oxygen blowing pressure is 0.6MPa for 3min each time, refining is continued for 10min after each oxygen blowing, and the melting temperature is controlled at 2350 ℃ under the control of the electric power system.
And casting the molten liquid obtained by melting into a sand mold, wherein the casting temperature is 2050 ℃, and the casting rate is 12-15 kg/s (the casting rate fluctuation does not exceed the range). And (3) carrying out heat preservation annealing after casting, wherein the annealing period is controlled to be 24 days from the casting temperature to 50 ℃ after casting is finished, removing the peripheral part of the casting body from the surface to the inside by 80mm after heat preservation annealing, and reserving the middle part of the casting body to obtain the low-resistivity electro-fused chromium corundum.
As shown in an SEM diagram of the low-resistivity electro-fused chrome corundum prepared by the embodiment referring to FIG. 1, it can be seen that the sizes of large grains of the aluminum-chromium solid solution can reach 289 mu m and 252 mu m, and the ultra-large aluminum-chromium solid solution grains are beneficial to reducing the resistivity of the electro-fused chrome corundum.
Example 2
The preparation method of the low-resistivity electro-fused chrome corundum provided by the embodiment comprises the following steps:
(1) 44.6% zircon sand, 23% industrial alumina powder, 3% rho-Al 2O3, 9% electrofused chromium, 15% chromium oxide green, 3% spinel and 2.4% sodium carbonate by mass percentage are weighed to obtain a mixed raw material. Wherein, the spinel consists of the following components in percentage by mass: 13.25% of MgO, 36.96% of Fe 2O346.38%,Al2O3 and the balance of impurities. The zircon sand consists of the following components in percentage by mass: zrO 265.49%,SiO2 32.58.58%, the balance being impurities. The mass percentage of Cr 2O3 in the electrofused chromium is 99.10 percent. The mass percentage of Cr 2O3 in the chromium green is 99.57 percent. The binding agent is sodium silicate aqueous solution with the mass fraction of 40%, and the mass of the binding agent is 8% of the sum of the mass of zircon sand, industrial alumina powder, rho-Al 2O3, chromium source, spinel and sodium carbonate.
And uniformly mixing the mixed raw materials with a binding agent, pressing for forming, drying to obtain a green body with the water content of 1.3wt.%, and crushing the green body until the granularity is less than 40mm.
(2) Melting the crushed rough blank obtained in the step (1), and controlling a melting power system: starting an arc at a high voltage of 340V, controlling the current to be 3600-4000A (the current fluctuation does not exceed the range), gradually reducing the voltage to 240V after melting for 30min, and controlling the current to be 6800-70000A (the current fluctuation does not exceed the range); oxygen is blown for 2 times in the melting process, the first oxygen blowing is performed after 120min of melting, the oxygen blowing pressure is 0.6MPa for 3min each time, the refining is continued for 10min after each time of oxygen blowing, and the melting temperature is controlled at 2400 ℃ under the control of the electric power system.
And casting the molten liquid obtained by melting into a sand mold, wherein the casting temperature is 2150 ℃, and the casting rate is 13-15 kg/s (the current fluctuation does not exceed the range). And (3) carrying out heat preservation annealing after casting, wherein the annealing period is controlled to be 25 days from the casting temperature to 50 ℃ after casting is finished, removing the peripheral part of the casting body from the surface to the inside 70mm after heat preservation annealing, and reserving the middle part of the casting body to obtain the low-resistivity electro-fused chromium corundum.
As shown in the SEM diagram of the low-resistivity electro-fused chrome corundum prepared by the embodiment shown in FIG. 2, the sizes of large grains of the aluminum-chromium solid solution can reach 251 μm and 331 μm, and the ultra-large aluminum-chromium solid solution grains are beneficial to reducing the resistivity of the electro-fused chrome corundum.
Example 3
The embodiment provides a preparation method of low-resistivity electro-fused chrome corundum, which comprises the following steps:
(1) 39% zircon sand, 24% industrial alumina powder, 3.5% rho-Al 2O3, 11% electrofused chromium, 16% chromium oxide green, 4% spinel and 2.5% sodium carbonate by mass percent are weighed to obtain a mixed raw material. Wherein, the spinel consists of the following components in percentage by mass: 13.49% of MgO, 36.24% of Fe 2O347.50%,Al2O3 and the balance of impurities. The zircon sand consists of the following components in percentage by mass: zrO 265.72%,SiO2 32.93.93%, the balance being impurities. The mass percentage of Cr 2O3 in the electrofused chromium is 99.12 percent. The mass percentage of Cr 2O3 in the chromium green is 99.76 percent. The binding agent is 40% of aluminum dihydrogen phosphate aqueous solution by mass, and the mass of the binding agent is 10% of the sum of the mass of zircon sand, industrial alumina powder, rho-Al 2O3, chromium source, spinel and sodium carbonate.
And uniformly mixing the mixed raw materials with a binding agent, pressing for forming, drying to obtain a green body with the water content of 1.4wt.%, and crushing the green body until the granularity is less than 40mm.
(2) Melting the crushed rough blank obtained in the step (1), and controlling a melting power system: starting an arc at a high voltage of 360V, controlling the current to be 3000-3200A (the current fluctuation does not exceed the range), after melting for 20min, gradually reducing the voltage to 180V, and controlling the current to be 7000-7500A (the current fluctuation does not exceed the range); oxygen is blown for 2 times in the melting process, the first oxygen blowing is performed after 110min of melting, the oxygen blowing pressure is 0.5MPa for 3min each time, the refining is continued for 8min after each oxygen blowing, and the melting temperature is controlled at 2300 ℃ under the control of the electric power system.
And casting the molten liquid obtained by melting into a sand mold, wherein the casting temperature is 2100 ℃, and the casting rate is 14-15 kg/s (the current fluctuation does not exceed the range). And (3) carrying out heat preservation annealing after casting, wherein the annealing period is controlled to be 25 days from the casting temperature to 50 ℃ after casting is finished, removing the peripheral part of the casting body from the surface to the inside by 50mm after heat preservation annealing, and reserving the middle part of the casting body to obtain the low-resistivity electro-fused chromium corundum.
Example 4
The embodiment provides a preparation method of low-resistivity electro-fused chrome corundum, which comprises the following steps:
(1) Weighing 39% of zircon sand, 20% of industrial alumina powder, 6% of rho-Al 2O3, 12% of electrofused chromium, 15% of chromium oxide green, 6% of spinel and 2% of sodium carbonate according to mass percentage to obtain a mixed raw material. Wherein, the spinel consists of the following components in percentage by mass: 12.54% of MgO, 2O345.39%,Al2O3 36.78% of Fe and the balance of impurities. The zircon sand consists of the following components in percentage by mass: zrO 265.61%,SiO2 32.91% and the balance of impurities. The mass percentage of Cr 2O3 in the electrofused chromium is 99.08 percent. The Cr 2O3 in the chromium green is 99.68 percent by mass. The binding agent is 40% of aluminum dihydrogen phosphate aqueous solution by mass, and the mass of the binding agent is 9% of the sum of the mass of zircon sand, industrial alumina powder, rho-Al 2O3, chromium source, spinel and sodium carbonate.
And uniformly mixing the mixed raw materials with a binding agent, pressing for forming, drying to obtain a green body with the water content of 1.4wt.%, and crushing the green body until the granularity is less than 40mm.
(2) Melting the crushed rough blank obtained in the step (1), and controlling a melting power system: starting an arc at a high voltage of 360V, controlling the current to be 3000-3200A (the current fluctuation does not exceed the range), after melting for 30min, gradually reducing the voltage to 230V, and controlling the current to be 7000-7200A (the current fluctuation does not exceed the range); oxygen is blown for 2 times in the melting process, the first oxygen blowing is performed after 120min of melting, the oxygen blowing pressure is 0.6MPa for 3min each time, the refining is continued for 15min after each oxygen blowing, and the melting temperature is controlled at 2380 ℃ under the control of the electric power system.
And casting the molten liquid obtained by melting into a sand mold, wherein the casting temperature is 1960 ℃, and the casting rate is 8-10 kg/s (the casting rate fluctuation does not exceed the range). And (3) carrying out heat preservation annealing after casting, wherein the annealing period is controlled to be 21 days from the casting temperature to 50 ℃ after casting is finished, removing the peripheral part of the casting body from the surface to the inside by 100mm after heat preservation annealing, and reserving the middle part of the casting body to obtain the low-resistivity electro-fused chromium corundum.
Comparative example 1
The preparation method of the electro-fused chrome corundum provided in the comparative example is basically the same as that in example 1, except that 45% zircon sand, 28% industrial alumina powder, 12% electro-fused chrome, 13% chrome oxide green and 2% soda ash are weighed according to mass percentage to obtain a mixed raw material. Namely, the raw materials for preparing the electro-fused chrome corundum do not contain rho-Al 2O3 and spinel.
Comparative example 2
The preparation method of the electro-fused chrome corundum provided by the comparative example is basically the same as that of the example 1, except that rho-Al 2O3 is replaced by industrial alumina powder with the same quality when the mixed raw material is prepared in the step (1), namely, the preparation raw material of the electro-fused chrome corundum does not contain rho-Al 2O3.
Comparative example 3
The preparation method of the electro-fused chrome corundum provided by the comparative example is basically the same as that of the example 1, except that when the mixed raw material is prepared in the step (1), spinel is replaced by raw materials containing MgO, fe 2O3 and Al 2O3 with equal mass, namely 42% zircon sand, 22% industrial alumina powder, 3% rho-Al 2O3, 11% electro-fused chrome, 14% chrome oxide green, 0.8% high-purity magnesia, 2.7% iron scale, 2.5% industrial alumina powder and 2% soda are weighed according to mass percentage, and the mixed raw material is obtained.
Experimental example
The low resistivity fused chrome corundum prepared in each example and the fused chrome corundum prepared in each comparative example were each examined for resistivity, and the results are shown in table 1.
The resistivity testing method comprises the following steps: according to the four-wire method: the method for measuring voltage by inputting current comprises the steps of measuring a resistance value according to R=U/I, and calculating the resistivity at each temperature point according to the resistivity rho=R×S/L, wherein S is the cross section area through which the current of the test sample passes, and L is the length of the sample through which the current of the test sample passes.
Table 1 resistivity test results
As can be seen from Table 1, by adopting specific raw materials and specific proportioning relationship, the electro-fused chrome corundum with low resistivity can be obtained.
While the invention has been illustrated and described with reference to specific embodiments, it is to be understood that the above embodiments are merely illustrative of the technical aspects of the invention and not restrictive thereof; those of ordinary skill in the art will appreciate that: modifications may be made to the technical solutions described in the foregoing embodiments, or equivalents may be substituted for some or all of the technical features thereof, without departing from the spirit and scope of the present invention; such modifications and substitutions do not depart from the spirit of the corresponding technical solutions; it is therefore intended to cover in the appended claims all such alternatives and modifications as fall within the scope of the invention.
Claims (10)
1. The low-resistivity electro-fused chrome corundum is characterized by being prepared from the following components in percentage by mass: 39% -45% of zircon sand, 20% -24% of industrial alumina powder, 3% -6% of rho-Al 2O3, 24% -27% of chromium source, 3% -6% of spinel and 2% -2.5% of sodium carbonate;
Wherein the chromium source comprises electrofused chromium and/or chromium green;
In the spinel, mgO is more than or equal to 12% and Fe 2O3≥40%,Al2O3 is more than or equal to 30% in percentage by mass.
2. The low-resistivity electro-fused chromite corundum according to claim 1 characterized in that in the zircon sand, zrO 2≥65%,SiO2 is not less than 32% by mass.
3. The low-resistivity electro-fused chromia-corundum according to claim 1, characterized in that in said electro-fused chromium, cr 2O3 is not less than 99% by mass.
4. The low-resistivity electro-fused chrome corundum according to claim 1, characterized in that Cr 2O3 is more than or equal to 99.5% in mass percent in the chrome green.
5. The low-resistivity electro-fused chromia-corundum according to claim 1, characterized in that the size of part of crystal grains of the solid solution of aluminum and chromium in the low-resistivity electro-fused chromia-corundum is 250-350 μm.
6. The low resistivity fused chrome corundum according to claim 1, characterized in that the low resistivity fused chrome corundum has a resistivity of 120 Ω.cm or less at 1100 ℃, a resistivity of 140 Ω.cm or less at 1000 ℃, a resistivity of 200 Ω.cm or less at 900 ℃, a resistivity of 250 Ω.cm or less at 800 ℃ and a resistivity of 480 Ω.cm or less at 700 ℃.
7. The method for preparing the low-resistivity electro-fused chromia-corundum according to any one of claims 1-6, comprising the steps of:
Uniformly mixing zircon sand, industrial alumina powder, rho-Al 2O3, a chromium source, spinel, sodium carbonate and a binding agent, and then performing compression molding and drying to obtain a rough blank; and (3) melting the rough blank, and then casting, insulating and annealing to obtain the low-resistivity electro-fused chromium corundum.
8. The method of producing low resistivity electro-fused chromia-corundum according to claim 7 characterized by meeting at least one of the following conditions:
(1) The binding agent comprises at least one of an aqueous silicate solution and an aqueous phosphate solution;
(2) The mass of the binding agent is 8% -10% of the sum of the mass of the zircon sand, the industrial alumina powder, the rho-Al 2O3, the chromium source, the spinel and the sodium carbonate;
(3) Further comprising the step of processing after the soak anneal, the processing comprising: and removing the peripheral part of the heat-insulating annealed casting body from the surface to the inside by 50-100 mm, and reserving the middle part of the casting body.
9. Refractory lining comprising a low resistivity electro-fused chromia-corundum according to any of claims 1-6.
10. A high temperature furnace comprising a refractory lining according to claim 9;
the high temperature furnace comprises a ceramic electric melting furnace.
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